Synthesis and luminescence properties of lead-halide based organic–inorganic layered perovskite compounds (CnH2n+1NH3)2PbI4 (n=4, 5, 7, 8 and 9)

This paper describes the synthesis and characterization of organic–inorganic layered perovskite compounds, (C_nH_2n+1NH₃)₂PbI₄ (n=4, 5, 7, 8 and 9). The effect of the number of carbon atoms on luminescence properties has been examined. Thin films of microcrystalline (C_nH_2n+1NH₃)₂PbI₄ fabricated by spin-coating are highly oriented, with the c-axis perpendicular to the substrate surface. Temperature-dependent optical absorption spectra reveal that (C_nH_2n+1NH₃)₂PbI₄ films (n=4, 7, 8 and 9) show the structural phase transitions. The excitonic structures of (C_nH_2n+1NH₃)₂PbI₄ vary with the number of carbon atoms of the alkyl chain length. At low temperatures below 100 K, the lowest-energy free-exciton band of (C_nH_2n+1NH₃)₂PbI₄ (n=7, 8 and 9) split into three fine-structure levels. In contrast to (C_nH_2n+1NH₃)₂PbBr₄ films, (C_nH_2n+1NH₃)₂PbI₄ (n=7, 8 and 9) shows no triplet exciton emission, but it shows the Stokes-shifted emission from bound excitons.     

Optical properties of natural quantum-well compounds (C6H5-CnH2n-NH3)2PbBr4 (n=1-4)

This paper describes the synthesis and characterization of self-assembled organic-inorganic layered perovskite compounds, (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ (n=1-4). the effect of the number of carbon atoms of the alkyl chain length (n) on optical properties has been studied. (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ films fabricated by spin-coating are microcrystalline form, single phase and oriented with the c-axis. Crystallinity, the maximum PL intensity and the lifetime of exciton emissions varied with the number of carbon atoms. the lowest-energy exciton splits into a few fine-structure levels at low temperatures. Time-resolved photoluminescence spectra reveal that (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ shows both singlet and triplet excitons. with decreasing temperature, triplet exciton emissions become dominant for (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ (n=1-3), while (C₆H₅-C₄H₈-NH₃)₂PbBr₄ shows mainly singlet exciton emissions. The intersystem crossing from excited singlet state to triplet state plays an important role in the relaxation process of excitons.     

X-ray diffraction, vibrational and photoluminescence studies of the self-organized quantum well crystal H3N(CH2)6NH3PbBr4

We have prepared new semiconductor H₃N(CH₂)₆NH₃PbBr₄ crystals which are self-assembled organic-inorganic hybrid materials. The grown crystals have been studied by X-ray diffraction, infrared absorption and Raman spectroscopy scattering. We found that the title compound, abbreviated 2C₆PbBr₄, crystallizes in a two-dimensional (2D) structure with a P2₁/a space group. In the inorganic semiconductor sub-lattice, the corner sharing PbBr₆ octahedra form infinite 2D chains. The organic C₆H₁₈N₂⁺ ions form the insulator barriers between the inorganic semiconductor layers. Such a packing leads to a self-assembled multiple quantum well structure. Raman and infrared spectra of the title compound were recorded in the 50-500 and 400-4000 cm⁻¹ frequency regions, respectively. The assignment of the observed Raman lines was performed by comparison with the homologous compounds. Transmission measurements on thin films of 2C₆PbBr₄, obtained by the spin coating method, revealed a strong absorption peak at 380 nm. Luminescence measurements showed an emission line at 402 nm associated with radiative recombinations of excitons confined within the PbBr₆ layers. The electron-hole binding energy is estimated at 180 meV.     

Exciton polariton in an organic–inorganic multiple-quantum-well crystal (C4H9NH3)2PbBr4

Exciton polariton in an organic–inorganic multiple-quantum-well (MQW) single crystal (C₄H₉NH₃)₂PbBr₄ at low temperature has been investigated by photoluminescence excitation (PLE), reflection, and time-resolved photoluminescence measurements. Since (C₄H₉NH₃)₂PbBr₄ has ideal two-dimensional excitons with an extremely large oscillator strength and forms self-organized MQW with a very short well-period (d～10 Å), polaritonic coupling among excitons is strong and extends over a large number of wells. Therefore, observed MQW polariton features were the same as those of bulk polaritons. We have also investigated relaxation dynamics of the MQW polariton in the same framework as discussions on bulk polaritons.     

Strongly enhanced free-exciton luminescence in microcrystalline CsPbCl3 films produced via the amorphous phase

High-quality CsPbCl₃ films composed of crystallites with narrow size distributions are achieved for various size levels, from microcrystalline to polycrystalline, by a novel heat-treatment method applied to the same amorphous films. Their photoluminescence is dominated by free-exciton emission at every size level without showing trapped-exciton emission in great contrast to the case for single crystals. The microcrystalline state shows more than an order of magnitude stronger free-exciton emission than the polycrystalline state, and exhibits intense stimulated emission under high-power excitation.     

Elaboration and characterization of organic–inorganic quantum wells impregnated on porous anodic alumina nanostructures

An organic–inorganic quantum well embedded on porous anodic alumina was synthesized and studied by MEB, AFM, optical absorption and photoluminescence. The morphology determined by the MEB and the AFM, shows that the size of the pores is about 10 nm for alumina evaporated on glass substrate and about 35 nm for alumina template prepared in sulfuric acid (H₂SO₄). The optical properties are characterized from absorption and photoluminescence spectra measured at room and low temperature. The measured spectral characteristics demonstrate the influence of the pore size on the emission of the organic–inorganic quantum well ((C₁₂H₂₅NH₃)₂PbI₄). An obvious blueshifted photoluminescence (PL) of (C₁₂H₂₅NH₃)₂PbI₄ in nanometer-sized pores was observed. It results in a better quantum confinement.     

Growth and optical, magnetic and transport properties of (C4H9NH3)2MCl4 organic-inorganic hybrid films (M = Cu, Sn)

Films of (C₄H₉NH₃)₂MCl₄ (M=Cu and Sn) organic-inorganic hybrid perovskites have been deposited in-situ by a single-source thermal ablation technique on glassy, crystalline and polymeric substrates. Independently of the substrate, the films were well crystallized, c-axis oriented and with a narrow rocking curve of the (0010) reflection (full width at half maximum <1°). The (0 0 ℓ) reflections were consistent with those of the bulk orthorhombic phases and the “c” lattice parameters were 30.85±0.05 and 32.35±0.05 Å, for the Cu- and the Sn-compound, respectively. (C₄H₉NH₃)₂CuCl₄ films had an optical absorption peak at 375 nm at room temperature. From the magnetic point of view they act as layered nanocomposites with a dominant ferromagnetic component localized in planes (2D magnetism). T_c was 7.3±0.1 K and a moderate easy-plane anisotropy was observed. The photoluminescence spectra of typical (C₄H₉NH₃)₂SnCl₄ films at 12 K had a broad yellow band, which did not correspond to any significant peak in the absorption spectrum. The films were semiconducting down to 250 K or, in the case of the best samples, down to 200 K and became insulating at lower temperature. The resistivity of the best films was (5±1) 10⁴ Ω cm at 300 K, and the energy gap was 1.11 eV. PACS 81.07.Pr; 81.15.Kk; 81.16.Dn     

Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

Extremely large binding energy of biexcitons in an organic-inorganic quantum-well material (C4H9NH3)2PbBr4

We have confirmed biexciton formation in an organic-inorganic hybrid quantum-well material (C₄H₉NH₃)₂PbBr₄ by photoluminescence and two-photon absorption measurements. The biexciton has extremely large binding energy, 60 meV, which to our knowledge is the largest value ever reported for a semiconductor. By analyzing the spectrum of biexciton luminescence, the biexciton gas temperature was found to be much higher than the bath temperature due to a higher local temperature arising from the large biexciton binding energy.     

衬底温度和硼掺杂对p型氢化微晶硅薄膜结构和电学特性的影响

以B₂H₆为掺杂剂,采用射频等离子体增强化学气相沉积技术在玻璃衬底上制备p型氢化微晶硅薄膜.研究了衬底温度和硼烷掺杂比对薄膜的微结构和暗电导率的影响.结果表明：在较高的衬底温度下很低的硼烷掺杂比即可导致薄膜非晶化;在实验范围内,随着衬底温度升高薄膜的晶化率单调下降,暗电导率先缓慢增加然后迅速下降,变化趋势与硼烷掺杂比的影响极为相似.最后着重讨论了p型氢化微晶硅薄膜的生长机理. 关键词： p型氢化微晶硅薄膜 衬底温度 晶化率 电导率     

Research of microstructural characteristics on nanocrystalline diamond by microwave plasma CVD

In this study, the nanocrystalline diamond (NCD) films were carried out by microwave plasma chemical vapor deposition (CVD) with CH₄/Ar/H₂ gas concoction on Si substrate at moderate temperatures. The characteristics of NCD films were evaluated using scanning electron microscopy, Raman spectroscopy, transmission electron microscopy, optical emission spectroscopy and optical contact angle meter. The analytical results revealed that C₂ radial was the dominant species in the deposited process. From TEM observation, the NCD films were formed via the etching of hydrocarbons and a small amount of H₂ content additive into gas mixture has improved the aggregation of the nucleation film to form the NCD films. The more hydrophobic surfaces imply that NCD films are the potential biomaterial in the application of article heart valve or stent.     

Flame structure studies of rich ethylene-oxygen-argon mixtures doped with CO2, or with NH3, or with H2O

Structures of several premixed ethylene-oxygen-argon rich flat flames burning at 50 mbar have been established by using molecular beam mass spectrometry in order to investigate the effect of CO₂, or NH₃, or H₂O addition on species concentration profiles. The aim of this study is to examine the eventual changes of profiles of detected hydrocarbon intermediates which could be considered as soot precursors (C₂H₂, C₄H₂, C₅H₄, C₅H₆, C₆H₂, C₆H₄, C₆H₆, C₇H₈, C₆H₆O, C₈H₆, C₈H₈, C₉H₈ and C₁₀H₈). The comparative study has been achieved on four flames with an equivalence ratio (f) of 2.50: one without any additive (F2.50), one with 15% of CO₂ replacing the same quantity of argon (F2.50C), one with 3.3% of NH₃ in partial replacement of argon (F2.50N) and one with 13% of H₂O in replacement of the same quantity of argon (F2.50H). The four flat flames have similar final flame temperatures (1800 K).CO₂, or NH₃, or H₂O addition to the fresh gas inlet causes a shift downstream of the flame front and thus flame inhibition. Endothermic processes CO₂ + H = CO + OH and H₂O + H = H₂ + OH are responsible of the reduction of the hydrocarbon intermediates in the CO₂ and H₂O added flames through the supplementary formation of hydroxyl radicals. It has been demonstrated that such processes begin to play at the end of the flame front and becomes more efficient in the burnt gases region.The replacement of some Ar by NH₃ is responsible only for a slight decrease of the maximum mole fraction of C₂H₂, but NH₃ becomes much more efficient for C₄H₂ and C₅ to C₁₀ species. Moreover, the efficiency of NH₃ as a reducing agent of C₅ to C₁₀ intermediates is larger than that of CO₂ and H₂O for equal quantities added.     

The formation and stability of co-crystalline NH3 · C2H2 aerosol particles

NH₃/C₂H₂ aerosols were formed in a bath gas cooling cell at cryogenic temperatures and studied using infrared spectroscopy. The infrared band shapes associated with these particles were quite different from those of the pure solids and vibrational shifts of up to 100 wavenumbers were observed. The phase of these particles was identified as a NH₃?·?C₂H₂ co-crystal and was found to be thermodynamically stable with respect to the solids of pure NH₃ and C₂H₂. Experiments with core–shell structures demonstrated that the co-crystalline phase could also be formed through a solid state reaction of pure NH₃ and C₂H₂ in aerosol particles. The results of this work are relevant to planetary atmospheres where both NH₃ and C₂H₂ are present, as the co-crystalline phase can readily form in mixed particles of these substances and its optical properties cannot be understood by simply considering the pure substances.     

The optoelectronic properties of silicon films deposited by inductively coupled plasma CVD

Hydrogenated amorphous and microcrystalline silicon films were deposited by inductively coupled plasma chemical vapor deposition (ICP-CVD) at low substrate temperatures using H₂-diluted SiH₄ as a source gas. High-density plasma generated by inductively coupled excitation facilitates the crystallization of silicon films at low temperatures, and microcrystalline silicon films were obtained at the substrate temperature as low as 180 °C. The columnar structure of the films becomes more and more compact with an increase of their crystallinity. The reduction of hydrogen content in the films causes a narrowing of the optical bandgap and an enhancement of the absorption with increasing the substrate temperature. The microcrystalline silicon films show two electronic transport mechanisms: one is related to the density of state distribution in the temperature region near room temperature and the other is the variable range hopping between localized electronic states close to the Fermi level below 170 K. A reasonable explanation is presented for the dependence of the optoelectronic properties on the microstructure of the silicon films. The films prepared at a substrate temperature of 300 °C have highly crystalline and compact columnar structure, high optical absorption coefficient and electrical conductivity, and a low hydrogen content of 3.8%.     

PHOTO- AND ELECTRO-LUMINESCENCE FROM HYDROGENATED AMORPHOUS SILICON CARBIDE FILMS PREPARED BY USING ORGANIC CARBON SOURCE

Hydrogenated amorphous silicon carbide (a-SiC:H) films were grown by using an organic source, xylene (C₈H₁₀), instead of methane (CH₄) in a conventional plasma enhanced chemical vapor deposition system. The optical band gap of these samples was increased gradually by changing the gas ratio of C₈H₁₀ to SiH₄. The film with high optical band gap was soft and polymer-like and intense photoluminescence were obtained. Room temperature electro-luminescence was also achieved with peak energy at 2.05 eV (600 nm) for the a-SiC:H film with optical band gap of 3.2 eV.     

Enhanced luminescence of CuCl microcrystals in a organic-inorganic hybrid matrix

γ-CuCl microcrystals were found to segregate in self-assembled (C_nH_2n+1NH₃)₂CuCl₄ hybrid organic-inorganic films deposited by single source thermal ablation. The microcrystals dispersed in the hybrid have sizes of 35 nm, as estimated from X-ray diffraction patterns. The UV photoluminescence efficiency of the embedded microcrystals is more than 100 times higher than that of CuCl films having similar crystallite sizes. PACS 78.67.Bf; 78.55.Hx; 81.07.Pr     

不同氮源制备CNx纳米管薄膜及其低场致电子发射性能

采用高温热解法，分别以氯化铵(NH₄Cl)和乙二胺(C₂H₈N₂)为氮源在洁净的硅片上沉积生长CN_x纳米管薄膜.利用扫描电子显微镜、高分辨率透射电子显微镜和拉曼光谱对CN_x纳米管进行形貌观察和表征.结果显示不同氮源制备出的CN_x纳米管薄膜的洁净度、有序度以及纳米管的结构明显不同.热解乙二胺(C₂H₈N₂)/二茂铁(C₁₀H₁₀Fe)制备出的结晶度较低的“竹节状” 结构CN_x纳米管平行基底表面有序生长，而且低场致电子发射性能优越,开启电场1.0V/μm，外加电场达到2.89V/μm时发射电流密度为860μA/cm². 关键词： x纳米管')" href="#">CN_x纳米管 高温热解 “竹节状”结构 场致发射     

Magnetic and structural properties of nitrified FINEMET powder using mechanical milling method

The magnetic and structural properties of FINEMET [Fe_73.5Si_13.5B₉Nb₃Cu₁ wt%] amorphous powder were investigated after nitrification and mechanical milling. Fe-based amorphous powder were nitrified and crystallized simultaneously at 550 °C using by ammonia (NH₃) gas. Nitrified powder exhibited iron nitride phase such as γ′-Fe₄N, Fe₃N, and α″-Fe₁₆N₂. Nitrified particles were more brittle than raw particles. As a result, nanometer-sized nitride powder was fabricated by high-energy ball milling method. The saturation magnetization (M_s) and coercivity (H_c) of nitrified powder were increased due to nitride phase.     

Polymorphism in organo-metallic bidimensional structures: The BIS (n-octylammonium) tetrachlorocadmate

Raman spectra, X-ray diffraction diagrams and differential scanning calorimetry show the existence of two structural phase transitions in crystalline (C₈H₁₇NH₃)₂ CdCl₄. The solid stable at low temperature is ordered, the alkylammonium chains are in extended configuration with probably a gauche bond in the proximity of the NH₃ group. The intermediate phase is characterized by a confonnational disorder and a modification of the crystalline structure. The number of internal rotations increases in the high temperature form; however the total transition entropy is lower than the value expected for a total “melting” of the chains.